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Direct method of reducing sodium bisuflite affixture of adhehyde or methyl ketone into correspondent alcohol

A technology of sodium bisulfite and addition products, applied in the direction of reduction and preparation of oxygen-containing functional groups, can solve the problems of low yield and decreased purity, and achieve the effects of convenient operation, high purity and high yield

Inactive Publication Date: 2004-09-01
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002] Aldehydes or methyl ketones can easily react with sodium bisulfite and generate corresponding sodium bisulfite adducts with high efficiency, and the purpose of purifying aldehydes or methyl ketones can be achieved by hydrolyzing this adduct but in the process of hydrolysis, due to acid or alkali treatment, the yield is often not high and the purity also decreases slightly, 〖J.Am.Chem.Soc.71,122(1949); J.Am.Chem. Soc.75, 1286(1953); J.Am.Chem.Soc.84, 373(1962); J.Am.Chem.Soc.88, 2811(1966); J.Am.Chem.Soc.100, 2226 (1978); J.Org.Chem.50, 2668(1985); J.Org.Chem.50, 1927(1985)〗

Method used

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  • Direct method of reducing sodium bisuflite affixture of adhehyde or methyl ketone into correspondent alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] The preparation of embodiment 1 benzyl alcohol

[0014] Add 15.9g (0.15mol) of sodium carbonate to 60ml of water, then add 4.1g (0.075mol) of potassium borohydride, add 21g (0.1mol) of benzaldehyde in batches at a temperature of 40-50°C for sodium bisulfite addition substance (or its aqueous solution), the reaction is exothermic, after the addition, it is reacted at 40-50°C for 1 hour, cooled, and the lower oil layer is separated, the water phase is extracted with dichloroethane, the oil phase is combined, and the oil phase is washed once with water. Dry over sodium sulfate and concentrate to obtain 9.9 g of benzyl alcohol with a yield of 92%.

[0015] 1 HNMR (300MHz, DMSO-d6) δ7.25-7.43 (m, 5H), 5.35 (t, 1H, J=5.8Hz), 4.62 (d, 2H, J=5.7Hz); MS (m / z, % ), 108 (M+, 100), 91 (16), 79 (89), 51 (16).

Embodiment 2

[0016] Example 2 Preparation of 3,4,5-trifluorobenzyl alcohol

[0017] Add 15.9g (0.15mol) sodium carbonate to 80ml water, then add 2.1g (0.039mol) potassium borohydride, control the temperature at 20-30°C, add dropwise 13.8g (0..05mol) 3,4,5- The solution of the sodium bisulfite adduct of trifluorobenzaldehyde and 70ml of water, the reaction is exothermic, after the addition, it is reacted at 40-50°C for 1 hour, cooled, and the lower oil layer is separated, and the water phase is extracted with dichloroethane. The oil phases were combined, washed once with water, dried over anhydrous sodium sulfate, and concentrated to obtain 7.97 g of 3,4,5-trifluorobenzyl alcohol with a yield of 93%.

[0018] 19 FNMR(282MHz, DMSO-d6)δ+60ppm(2F)+89ppm(1F); 1 HNMR (300MHz, DMSO-d6) δ7.08-7.16 (m, 2H), 5.47 (s, 1H), 4.52 (s, 2H); MS (m / z, %), 175 (M+, 0.45), 162 (100), 145(69), 141(63), 133(59), 113(37).

Embodiment 3

[0019] Example 3 Preparation of 2-fluoro-4-bromobenzyl alcohol

[0020] Add 31.8g (0.3mol) of sodium carbonate to 100ml of water, then add 4.2g (0.078mol) of potassium borohydride, add dropwise 30.6g (0.1mol) of 2-fluoro-4-bromobenzaldehyde at a temperature of 35-40°C The solution of sodium bisulfite adduct and 100ml water, the reaction is exothermic, after the addition, react at 40-50°C for 1 hour, cool, separate the lower oil layer, extract the water phase with dichloroethane, combine the oil phase, The oil phase was washed once with water, dried over anhydrous sodium sulfate, and concentrated to obtain 19.3 g of 2-fluoro-4-bromobenzyl alcohol, with a yield of 95%.

[0021] 19 FNMR (282MHz, DMSO-d6) δ+40ppm; 1 HNMR (300MHz, DMSO-d6) δ7.34-7.45 (m, 3H), 5.38 (t, 1H, J=5.7Hz), 4.52 (s, 2H); MS (m / z, %), 204 (M+ , 78), 189(21), 175(15), 125(100), 107(22), 97(88).

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Abstract

The invention relates to a method for directly reducing addition product of sodium hydrogen sulfite which is produced by reaction of aldehyde or methyl ketone and sodium hydrogen sulfite into correspondent alcohol. It is characterized by that after said addition product is extracted and purified, it can be directly reduced into correspondent alcohol by using hydroborates or other reducing agent. Said method is applicable to preparation of alcohol which is difficult to be purified, and said alcohol possesses high purity.

Description

technical field [0001] The invention provides a method for directly reducing the sodium bisulfite addition product of aldehydes or methyl ketones to alcohols, wherein the aldehydes can be aliphatic aldehydes and aromatic aldehydes; the ketones are alkyl methyl ketones or aryl methyl ketones ketone. Background technique [0002] Aldehydes or methyl ketones can easily react with sodium bisulfite and generate corresponding sodium bisulfite adducts with high efficiency, and the purpose of purifying aldehydes or methyl ketones can be achieved by hydrolyzing this adduct but in the process of hydrolysis, due to acid or alkali treatment, the yield is often not high and the purity also decreases slightly, 〖J.Am.Chem.Soc.71,122(1949); J.Am.Chem. Soc.75, 1286(1953); J.Am.Chem.Soc.84, 373(1962); J.Am.Chem.Soc.88, 2811(1966); J.Am.Chem.Soc.100, 2226 (1978); J.Org.Chem.50, 2668(1985); J.Org.Chem.50, 1927(1985)〗. In order to produce alcohols from aldehydes or methyl ketones with high yi...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C29/132
Inventor 张芳江司玉贵姜标
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI